JP2014095896A - Transparent conductive film and use of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent conductive film having blocking resistance and, at the same time, having good transparency and antiglare property; a display element using the transparent conductive film; and an image display device including the display element.SOLUTION: A transparent conductive film for a display element which includes a black matrix having a polygonal opening and which has a definition of 150 ppi or more is provided. The film comprises a transparent polymer substrate, a transparent conductive layer disposed on a first major surface side of the transparent polymer substrate, and a cured resin layer disposed at least either between the transparent polymer substrate and the transparent conductive layer or on a second major surface at the opposite side to the first major surface of the transparent polymer substrate. The outermost surface layer of the film where the cured resin layer is formed includes a flat portion and a protruding portion. A height of the protruding portion is larger than 10 nm from the flat portion; and a maximum diameter of a cross-sectional shape, which is formed by a plane parallel to the flat portion intersecting the protruding portion at a distance of 10 nm from the flat portion, is smaller than a minimum of distances between two non-adjacent sides of the opening of the black matrix.

Description

  The present invention relates to a transparent conductive film and its use.

  Transparent conductive films in which a transparent conductive thin film is formed on a transparent polymer substrate are widely used for solar cells, inorganic EL elements, transparent electrodes for organic EL elements, electromagnetic wave shielding materials, touch panels, and the like. In particular, in recent years, the rate of mounting touch panels on electronic devices such as mobile phones, mobile game devices, and tablet PCs has increased, and the demand for transparent conductive films has been rapidly expanding.

  As a transparent conductive film used for a touch panel or the like, a conductive metal oxide film such as indium-tin composite oxide (ITO) was formed on a flexible transparent polymer substrate such as a polyethylene terephthalate film. Things are widely used. In such a transparent conductive film, the transparent polymer substrate is cured on the substrate for the purpose of preventing the scratch existing from the beginning from being visually recognized or preventing the scratch that may occur in the manufacturing process. A resin layer (hard coat layer) may be formed.

  In general, since the cured resin layer has high surface smoothness, the transparent conductive film provided with the cured resin layer on the surface of the substrate has problems such as insufficient slipperiness and blocking resistance, and poor handling properties. Yes. Also, when producing and processing a film, from the viewpoint of productivity and handling properties, it is often a wound body in which a long sheet is wound in a roll shape. When the film is conveyed in a roll or wound as a wound body, the film surface is likely to be scratched, and further, the winding property tends to be inferior when wound into a roll. Moreover, when a film having poor blocking resistance is wound into a roll, blocking is likely to occur during storage and transportation of the wound body.

  From the viewpoint of solving such a problem, a technique for improving slipperiness and blocking resistance by forming fine irregularities on the surface of a transparent plastic film has been proposed (Patent Document 1).

JP 2003-45234 A

  However, as described in Patent Document 1, when fine irregularities are formed on a plastic film, appearance defects such as loss of transparency of the transparent conductive film are caused due to light scattering by the irregularities. There is a case.

  On the other hand, by adding relatively large particles (for example, particles larger than the thickness of the cured resin layer) to the cured resin layer to form a bulge, while ensuring blocking resistance with a small amount of addition, A measure to maintain high transparency by adding a small amount is also conceivable.

  However, it has been found that when a transparent conductive film using the above-described particles is incorporated in a liquid crystal display or the like, which has recently been improved in definition, glare occurs and appearance may be impaired.

  In view of the above viewpoint, the present invention provides a transparent conductive film having anti-blocking properties and good transparency and antiglare properties, a display element using the same, and an image display device including the display element. With the goal.

  As a result of intensive studies to solve the above problems, the present inventors have found that a transparent conductive film having an outermost surface layer having raised portions of a specific size corresponding to a high-definition display can achieve the above object. Invented.

That is, the present invention is a transparent conductive film for a display element having a definition of 150 ppi or more comprising a black matrix having a polygonal opening,
A transparent polymer substrate;
A transparent conductive layer provided on the first main surface side of the transparent polymer substrate;
A cured resin layer provided between the transparent polymer substrate and the transparent conductive layer and on at least one of the second principal surface opposite to the first principal surface of the transparent polymer substrate;
A flat portion and a raised portion are formed on the surface of the outermost surface layer on the side where the cured resin layer is formed,
The height of the raised portion is larger than 10 nm from the flat portion,
The maximum diameter of the cross-sectional shape formed by intersecting the raised portion at a position parallel to the flat portion at a distance of 10 nm from the flat portion is based on the minimum value of the distance between two non-adjacent sides of the opening of the black matrix. Is a small transparent conductive film.

  In the said transparent conductive film, favorable blocking resistance can be exhibited by the protruding part in the surface of the outermost surface layer. In addition, since it is excellent in the winding property of the film, it is easy to produce a wound body obtained by winding a long sheet into a roll shape. And can also contribute to waste reduction. In addition, since the flat portion and the raised portion coexist instead of forming fine irregularities on the entire surface of the cured resin layer, the raised portion is formed in the flat portion even in the outermost surface layer, As a result, high transparency of the transparent conductive film can be maintained. Further, the maximum diameter of the cross-sectional shape of the base of the raised portion of the outermost surface layer (region having a height of 10 nm from the flat portion) is made smaller than the minimum value of the distance between two adjacent sides of the black matrix opening of the display element. Therefore, even when incorporated in a high-definition display element of 150 ppi or more, it is possible to prevent glare and cope with higher definition of the display element.

  The cured resin layer has a base flat portion and a base raised portion on a surface, the flat portion of the outermost surface layer is formed due to the base flat portion, and the raised portion is caused by the base raised portion. It is preferable to be formed. By providing a base flat part and a base bulge in a cured resin layer that is relatively easy to increase in film thickness and surface processing, the base flat part and the base bulge are also copied to the outermost surface layer of the transparent conductive film. A flat portion and a raised portion can be easily provided.

  It is preferable that the cured resin layer includes particles, and the base protruding portion is formed due to the particles. As a result, the base raised portion can be formed efficiently and simply, and as a result, the raised portion can be formed on the outermost surface layer, and transparency can be easily improved (low haze).

  By making the thickness of the base flat portion of the cured resin layer smaller than the mode particle diameter of the particles, haze can be reduced and transparency can be further improved.

  In the transparent conductive film, the cured resin layer is provided between the transparent polymer substrate and the transparent conductive layer, and a refractive index adjustment layer is provided between the cured resin layer and the transparent conductive layer. Furthermore, you may provide.

  The haze of the transparent conductive film is preferably 5% or less. Thereby, high transparency can be exhibited and favorable visibility can be ensured.

  The transparent conductive film may further include a transparent conductive layer provided on the second main surface side opposite to the first main surface side of the transparent polymer substrate.

  You may use the said transparent conductive film in the form of a long sheet form, and the transparent conductive film winding body which wound this in roll shape.

  The present invention includes a touch panel including the transparent conductive film, a display element including the transparent conductive film having a definition of 150 ppi or more, and an image display device in which the display element having a definition of 150 ppi or more and the touch panel are stacked. Is also included. According to the transparent conductive film, it is possible to deal with display elements and the like that are becoming higher in definition, and a clearer image can be obtained.

It is typical sectional drawing of the transparent conductive film which concerns on one Embodiment of this invention. It is a schematic plan view of the black matrix in a display element. It is an enlarged plan view which shows an example of the opening part of a black matrix typically. It is an enlarged plan view which shows typically another example of the opening part of a black matrix. FIG. 6 is a schematic plan view schematically showing the relationship between the maximum diameter of the cross-sectional shape of the raised portion of the outermost surface layer and the minimum value of the distance between two non-adjacent sides of the opening of the black matrix. It is sectional drawing which shows typically the relationship between the maximum diameter of the cross-sectional shape of the protruding part of an outermost surface layer, and the minimum value of the distance between the two sides which the opening part of a black matrix does not adjoin. It is a schematic diagram which shows an example of the largest diameter of the cross-sectional shape of the protruding part of an outermost surface layer.

  An embodiment of the present invention will be described below with reference to the drawings. FIG. 1 is a cross-sectional view schematically showing one embodiment of the transparent conductive film of the present invention. In the transparent conductive film 10, a transparent conductive layer 3 is formed on the first main surface 1 a side which is one main surface of the transparent polymer substrate 1, and the transparent polymer substrate 1 and the transparent conductive layer 3 are formed. And a cured resin layer 2a, 2b containing particles 5 on the second principal surface 1b side which is the other principal surface of the transparent polymer substrate 1 (hereinafter referred to as “cured resin layer 2” together) Is formed). Further, a refractive index adjusting layer 4 is formed between the cured resin layer 2 a and the transparent conductive layer 3. In the transparent conductive film 10, since the cured resin layers 2 a and 2 b are formed on both surfaces of the transparent polymer substrate 1, the transparent conductive layer 3 is the outermost surface on the first main surface 1 a side of the transparent polymer substrate 1. The cured resin layer 2b is the outermost surface layer on the second main surface 1b side.

  Moreover, the cured resin layer 2a has the base flat part 21 and the base protruding part 22 on the surface. In the transparent conductive film 10, since the thicknesses of the refractive index adjustment layer 4 and the transparent conductive layer 3 are made thinner than the thickness of the cured resin layer 2a, they are refracted so as to follow the surface of the cured resin layer 2a. The rate adjusting layer 4 and the transparent conductive layer 3 are laminated. Thereby, the transparent conductive layer 3 which is the outermost surface layer has the flat portion 31 and the raised portion 32 due to the base flat portion 21 and the base raised portion 22 of the cured resin layer 2a, respectively. Similarly, the cured resin layer 2b also has a flat portion and a raised portion.

  The height of the raised portion 32 of the transparent conductive layer 3 is larger than 10 nm with respect to the flat portion 21, but is preferably 100 nm or more and 3 μm or less, more preferably 200 nm or more and 2 μm or less, and further preferably 300 nm or more and 1.5 μm or less. preferable. By setting the height of the raised portion 32 in the above range, the anti-blocking property can be satisfied, the glare can be sufficiently reduced, and the haze increase can be sufficiently suppressed.

  In the transparent conductive film 10, the maximum diameter near the skirt of the raised portion of the outermost surface layer (in this embodiment, the transparent conductive layer 3 and the cured resin layer 2b) on the side where the cured resin layer 2 is formed, and the display element The minimum value of the distance between two non-adjacent sides of the opening of the black matrix satisfies a specific relationship. This configuration will be described below.

The black matrix 11 is used as a member for controlling the transmission of light of R (red), G (green), and B (blue) corresponding to each pixel (sub-pixel) of a color filter in a liquid crystal display element, for example. As representatively shown in FIG. 2, a rectangular member in which rectangular openings O ₁ are formed in a matrix. Note that the pixel density of the display element is defined by the size of the opening O ₁ . The opening O ₁ has a rectangle composed of two sets of two parallel sides facing each other. Accordingly, the opening O ₁ has short sides and long sides as two sides that are not adjacent to each other. In the opening O ₁ , the distance between the long sides is shorter than the distance between the short sides and the distance between the long sides. Therefore, the minimum value of the distance between two non-adjacent sides is the distance L between the long sides. ₁

3A and 3B are plan views showing other forms of the opening. The shape of the opening O ₂ shown in FIG. 3A is a parallelogram in plan view, and the minimum value of the distance between two non-adjacent sides is the distance L ₂ between the long sides. Also, the shape of the opening O ₃ shown in FIG. 3B is a shape in which two parallelograms (congruent to each other in FIG. 3B) are in contact with each other in the plan view so as to form a V shape as a whole. Here, the opening O ₃ is constituted by three sets of two parallel sides facing each other. In this case, theoretically, there are six combinations of two sides that are not adjacent (As shown in FIG. 3B, when A to F are assigned to each side and duplication is removed in consideration of symmetry, A-C, A inter -D, between a-E, between B-D, between B-E, 6 pairs between B-F), but will be present, between the out distance _{L 3} between the B-F are not adjacent two sides This corresponds to the minimum distance. The minimum value of the distance between two non-adjacent sides can be obtained based on the same idea for the openings of other forms.

4A and 4B are schematic views showing only a black matrix constituting the display element when the transparent conductive film and the display element are laminated, and showing the black matrix and the transparent conductive film as a laminate. 4A is a schematic view of the laminate viewed from the black matrix 11 side, and FIG. 4B is a cross-sectional view taken along the line XX of FIG. 4A. In the transparent conductive film 10, the maximum diameter of the cross-sectional shape C ₁ formed by the plane P parallel to the flat portion 31 of the transparent conductive layer 3, which is the outermost surface layer, intersecting the raised portion 32 at a position 10 nm away from the flat portion 31. d ₁ is smaller than the minimum value L ₁ of the distance between two non-adjacent sides (here, between the long sides) in the opening O ₁ of the black matrix 11 of the display element. For convenience of explanation, in FIG. 4A, the entire raised portion 32 is not shown inside the opening O ₁ , but only the cross-sectional shape C ₁ is shown. In FIG. 4B, the transparent portion of FIG. Of the constituent elements of the conductive film, only the transparent polymer substrate 1 and the contour 3a of the surface of the transparent conductive layer 3 on the first main surface 1a side of the transparent polymer substrate 1 are shown. Of course, since the cured resin layer 2b is provided as the outermost surface layer also on the second main surface 1b side of the transparent polymer base material, the same relationship as described above holds for the raised portions in the cured resin layer 2b.

  The maximum diameter of the cross-sectional shape of the base of the bulge is only required to be smaller than the minimum value of the distance between two non-adjacent sides of the opening of the black matrix, and the maximum diameter is the minimum of the distance between two non-adjacent sides of the opening. It is preferably 10 to 95% of the value, and more preferably 10 to 80%.

  In the transparent conductive film 10, the size near the base of the raised portion of the outermost surface layer and the opening size of the opening portion of the black matrix have a specific relationship, so that a high-definition display element is provided while providing blocking resistance Glittering can be prevented even in combination with.

  4A and 4B, the transparent conductive layer 3 and the black matrix 11 are laminated so that they face each other. However, the lamination form is not limited to this, and the second main surface of the transparent polymer substrate 1 is not limited thereto. The laminated form may be such that the cured resin layer 2b on the 1b side and the black matrix 11 face each other. In any laminated form, the maximum diameter of the cross-sectional shape of the raised portion of the outermost surface layer is smaller than the minimum value of the distance between two non-adjacent sides of the opening of the black matrix.

FIG. 5 is a schematic diagram showing another form of a cross-sectional shape formed by intersecting a surface parallel to the flat portion and the raised portion. Sectional shape C ₁ in FIG. 4A whereas a circular cross-sectional shape C ₂ in FIG. 5 is an elliptical. Maximum diameter d ₂ in this case coincides with the major axis of the ellipse.

  The haze of the transparent conductive film is not particularly limited as long as the required transparency can be secured, but is preferably 5% or less, more preferably 4% or less, and even more preferably 3% or less. In addition, although the lower limit of haze is preferably 0%, it is generally often 0.3% or more due to the presence of a raised portion of the outermost surface layer.

<Transparent polymer substrate>
Although it does not restrict | limit especially as the transparent polymer base material 1, The various plastic film which has transparency is used. For example, the materials include polyester resins, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, polynorbornene resins, and other polycycloolefin resins (meta ) Acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, polyarylate resins, polyphenylene sulfide resins and the like. Of these, polyester resins, polycarbonate resins, and polyolefin resins are particularly preferable.

  The thickness of the transparent polymer substrate 1 is preferably in the range of 2 to 200 μm, and more preferably in the range of 20 to 180 μm. When the thickness of the transparent polymer substrate 1 is less than 2 μm, the mechanical strength of the transparent polymer substrate 1 is insufficient, and the operation of continuously forming the transparent conductive layer 4 by making the film substrate into a roll shape. It can be difficult. On the other hand, if the thickness exceeds 200 μm, the scratch resistance of the transparent conductive layer 4 and the dot characteristics for touch panels may not be improved.

  The transparent polymer substrate 1 is a cured resin formed on the film substrate by subjecting the surface to an etching treatment or undercoating treatment such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical conversion, and oxidation in advance. You may make it improve adhesiveness with a layer, a transparent conductive layer, etc. In addition, before forming the cured resin layer or the transparent conductive layer, the surface of the film substrate may be dust-removed and cleaned by solvent cleaning or ultrasonic cleaning as necessary.

<Curing resin layer>
As described above, the cured resin layer 2 has the base flat portion 21 and the base raised portion 22 on the surface. The base raised portion 22 is formed due to the particles 5 included in the cured resin layer 2. The height of the base raised portion 22 is larger than 10 nm with respect to the base flat portion 22, preferably 100 nm or more and 3 μm or less, more preferably 200 nm or more and 2 μm or less, and further preferably 300 nm or more and 1.5 μm or less. . By setting the height of the base raised portion 22 in the above range, a predetermined amount is applied to the outermost surface layer (the transparent conductive layer 3 on the first main surface 1a side in FIG. 1 and the cured resin layer 2b on the second main surface 1b side). As a result, a raised portion can be provided, and as a result, the anti-blocking property of the transparent conductive film 10 can be satisfied, and at the same time, the glare can be sufficiently reduced and the increase in haze can be sufficiently suppressed.

  Although the thickness of the base flat part 21 of the cured resin layer 2 is not particularly limited, it is preferably 200 nm or more and 30 μm or less, more preferably 500 nm or more and 10 μm or less, and further preferably 800 nm or more and 5 μm or less. . If the thickness of the base flat portion of the cured resin layer is too small, precipitation of low molecular weight components such as oligomers from the transparent polymer base material cannot be suppressed, and a transparent conductive film or a touch panel using the same There is a tendency for the visibility to deteriorate. On the other hand, when the thickness of the flat base portion of the cured resin layer is excessively large, the transparent conductive film tends to curl with the cured resin layer forming surface as the inside due to heating during crystallization of the transparent conductive layer or assembly of the touch panel There is. Therefore, when the thickness of the base flat part of a cured resin layer is large, it is a problem different from blocking resistance and slipperiness, and there exists a tendency for it to be inferior to the handleability of a film. In addition, in this specification, the thickness of the base flat part of a cured resin layer refers to the average thickness in the base flat part of a cured resin layer.

  Furthermore, it is preferable to make the thickness of the base flat portion 21 of the cured resin layer 2 smaller than the mode particle diameter of the particles 5 because haze can be reduced and transparency can be further improved.

  The mode particle diameter of the particles can be appropriately set in consideration of the relationship between the size of the protruding portion of the outermost surface layer and the thickness of the base flat portion 21 of the cured resin layer 2, and is not particularly limited. In addition, from the viewpoint of sufficiently imparting blocking resistance to the transparent conductive film and sufficiently suppressing increase in haze, the mode particle diameter of the particles is preferably 500 nm or more and 30 μm or less, and 800 nm or more and 20 μm or less. It is more preferable that it is 1 μm or more and 10 μm or less. In the present specification, “mode particle diameter” means a particle diameter showing the maximum value of particle distribution, and using a flow type particle image analyzer (product name “FPIA-3000S” manufactured by Sysmex). , By measuring under predetermined conditions (Sheath solution: ethyl acetate, measurement mode: HPF measurement, measurement method: total count). The measurement sample is prepared by diluting the particles to 1.0% by weight with ethyl acetate and uniformly dispersing the particles using an ultrasonic cleaner.

  The particles may be either polydisperse particles or monodisperse particles, but monodisperse particles are preferred in view of the ease of providing the raised portions and the antiglare property. In the case of monodisperse particles, the particle size and mode particle size can be regarded as substantially the same.

  The content of the particles in the cured resin layer is preferably 0.01 to 5 parts by weight, more preferably 0.02 to 1 part by weight with respect to 100 parts by weight of the solid content of the resin composition, More preferably, it is 0.05-0.5 weight part. When the content of the particles in the cured resin layer is small, there is a tendency that a base raised portion sufficient to impart blocking resistance and slipperiness to the surface of the cured resin layer is hardly formed. On the other hand, if the content of the particles is too large, the haze of the transparent conductive film increases due to light scattering by the particles, and the visibility tends to decrease. Moreover, when the content of the particles is too large, streaks are generated during the formation of the cured resin layer (at the time of application of the solution), and visibility may be impaired, or the electrical characteristics of the transparent conductive layer may be uneven. There is a case.

(Resin composition)
As the resin composition for forming the cured resin layer 2, particles can be dispersed, and a transparent film having sufficient strength as a film after the cured resin layer is formed can be used without particular limitation. Examples of the resin to be used include thermosetting resins, thermoplastic resins, ultraviolet curable resins, electron beam curable resins, and two-component mixed resins. Among these, simple curing treatment by ultraviolet irradiation is possible. An ultraviolet curable resin capable of efficiently forming a film by a processing operation is preferable.

  Examples of the ultraviolet curable resin include polyester-based, acrylic-based, urethane-based, amide-based, silicone-based, and epoxy-based resins, and include ultraviolet curable monomers, oligomers, polymers, and the like. Examples of the ultraviolet curable resin preferably used include those having an ultraviolet polymerizable functional group, particularly those containing an acrylic monomer or oligomer component having 2 or more, particularly 3 to 6 functional groups. Further, an ultraviolet polymerization initiator is blended in the ultraviolet curable resin.

  In addition to the materials described above, additives such as leveling agents, thixotropic agents, and antistatic agents can be used as the resin layer forming material. Use of a thixotropic agent is advantageous for the formation of protruding particles on the surface of a fine irregular shape. Examples of the thixotropic agent include silica and mica of 0.1 μm or less. The content of these additives is usually about 15 parts by weight or less, preferably 0.01 to 15 parts by weight with respect to 100 parts by weight of the ultraviolet curable resin.

(particle)
As particles contained in the cured resin layer 2, those having transparency such as various metal oxides, glass, and plastic can be used without particular limitation. For example, inorganic particles such as silica, alumina, titania, zirconia, calcium oxide, polymethylmethacrylate, polystyrene, polyurethane, acrylic resin, acrylic-styrene copolymer, benzoguanamine, melamine, polycarbonate, or other cross-linked or uncrosslinked polymers. Examples include crosslinked organic particles and silicone particles. The particles can be used by appropriately selecting one type or two or more types, but organic particles are preferable. The organic particles are preferably acrylic resins from the viewpoint of refractive index.

(Coating composition)
The coating composition used to form the cured resin layer includes the resin, particles, and solvent described above. Moreover, a coating composition can add various additives as needed. Examples of such additives include conventional additives such as antistatic agents, plasticizers, surfactants, antioxidants, and ultraviolet absorbers.

  A coating composition is prepared by mixing said resin and particle | grains with a solvent, an additive, a catalyst, etc. as needed. The solvent in the coating composition is not particularly limited, and is appropriately selected in consideration of the resin to be used, the material used as the base of the coating, the coating method of the composition, and the like. Specific examples of the solvent include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and ethylene glycol. Ether solvents such as diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole and phenetol; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate and ethylene glycol diacetate; dimethylformamide, diethylformamide, N -Amide solvents such as methylpyrrolidone; methyl cellosolve, ethyl Cellosolve, cellosolve-based solvents such as butyl cellosolve; methanol, ethanol, alcohol solvents such as propanol; and the like; dichloromethane, halogenated solvents such as chloroform. These solvents may be used alone or in combination of two or more. Of these solvents, ester solvents, ether solvents, alcohol solvents and ketone solvents are preferably used.

  In the coating composition, the particles are preferably dispersed in a solution. As a method for dispersing particles in a solution, various known methods such as a method of adding particles to a resin composition solution and mixing, a method of adding particles dispersed in a solvent in advance to a resin composition solution, and the like. Can be adopted.

  The solid concentration of the coating composition is preferably 1% by weight to 70% by weight, more preferably 2% by weight to 50% by weight, and most preferably 5% by weight to 40% by weight. If the solid content concentration is too low, the unevenness of the base bulge portion on the surface of the cured resin layer increases in the drying step after coating, and the haze of the portion where the base bulge portion on the surface of the cured resin layer is large may increase. . On the other hand, if the solid content concentration is too high, the contained components are likely to aggregate, and as a result, the aggregated portion becomes obvious and the appearance of the transparent conductive film may be impaired.

(Coating and curing)
A cured resin layer is formed by apply | coating said coating composition on a base material. Application of the coating composition onto the transparent polymer substrate 1 is performed on both sides of the substrate in the case of this embodiment as shown in FIG. In addition, the coating composition may be performed directly on the transparent polymer substrate 1 or may be performed on an undercoat layer or the like formed on the transparent polymer substrate 1.

  The application method of the coating composition can be selected as appropriate according to the coating composition and the state of the painting process. For example, the dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure method It can be applied by a coating method, a die coating method or an extrusion coating method.

A cured resin layer can be formed by curing the coating film after applying the coating composition. When the resin composition is photocurable, it can be cured by irradiating light using a light source that emits light having a wavelength as required. As the irradiation light, for example, the exposure amount 150 mJ / cm ² or more optical, preferably using light of ^{200mJ / cm 2 ~1000mJ / cm 2} . The wavelength of the irradiation light is not particularly limited, and for example, irradiation light having a wavelength of 380 nm or less can be used. In addition, you may heat in the case of a photocuring process.

<Transparent conductive layer>
The constituent material of the transparent conductive layer 3 is not particularly limited, and is at least selected from the group consisting of indium, tin, zinc, gallium, antimony, titanium, silicon, zirconium, magnesium, aluminum, gold, silver, copper, palladium, and tungsten. A metal oxide of one kind of metal is preferably used. The metal oxide may further contain a metal atom shown in the above group, if necessary. For example, indium oxide (ITO) containing tin oxide and tin oxide (ATO) containing antimony are preferably used.

The thickness of the transparent conductive layer 3 is not particularly limited, but in order to obtain a continuous film having good conductivity with a surface resistance of 1 × 10 ³ Ω / □ or less, the thickness is preferably 10 nm or more. When the film thickness becomes too thick, the transparency is lowered, and it is preferably 15 to 35 nm, more preferably in the range of 20 to 30 nm. If the thickness of the transparent conductive layer 3 is less than 15 nm, the electrical resistance of the film surface becomes high and it becomes difficult to form a continuous film. Further, when the thickness of the transparent conductive layer 3 exceeds 35 nm, the transparency may be lowered.

  The formation method of the transparent conductive layer 3 is not specifically limited, A conventionally well-known method is employable. Specific examples include dry processes such as vacuum deposition, sputtering, and ion plating. In addition, an appropriate method can be adopted depending on the required film thickness. In addition, as shown in FIG. 1, when forming the transparent conductive layer 3 on the cured resin layer 2a formation surface side, if the transparent conductive layer 3 is formed by a dry process such as a sputtering method, the surface of the transparent conductive layer 3 is The shapes of the base flat portion and the base raised portion on the surface of the cured resin layer 2a as the underlying layer are substantially maintained. Therefore, even when the transparent conductive layer 3 is formed on the cured resin layer 2a, blocking resistance and easy slipperiness can be suitably imparted to the surface of the transparent conductive layer 3.

  The transparent conductive layer 3 can be crystallized by performing a heat annealing treatment (for example, at 80 to 150 ° C. for about 30 to 90 minutes in an air atmosphere) as necessary. By crystallizing the transparent conductive layer, transparency and durability are improved in addition to the resistance of the transparent conductive layer being lowered. By setting the thickness of the cured resin layer 2a in the transparent conductive film 10 within the above range, the occurrence of curling is suppressed even during the heat annealing treatment, and the handling property is excellent.

  The transparent conductive layer 3 may be patterned by etching or the like. For example, in a transparent conductive film used for a capacitive touch panel or a matrix resistive touch panel, the transparent conductive layer 3 is preferably patterned in a stripe shape. In addition, when patterning the transparent conductive layer 3 by etching, if the transparent conductive layer 3 is crystallized first, patterning by etching may be difficult. Therefore, it is preferable to perform the annealing treatment of the transparent conductive layer 3 after patterning the transparent conductive layer 3.

<Refractive index adjustment layer>
In the transparent conductive film 10 of the present embodiment, the refractive index adjustment layer 4 is provided between the cured resin layer 2a and the transparent conductive layer 3 for the purpose of controlling the adhesion and reflection characteristics of the transparent conductive layer. ing. The refractive index adjustment layer may be one layer or two or more layers. The refractive index adjusting layer is formed of an inorganic material, an organic material, or a mixture of an inorganic material and an organic material. As a material for forming the refractive index adjustment layer, NaF, Na ₃ AlF ₆ , LiF, MgF ₂ , CaF _2, SiO ₂ , LaF ₃ , CeF ₃ , Al ₂ O ₃ , TiO ₂ , Ta ₂ O ₅ , ZrO ₂ , ZnO, ZnS, SiO _x (x is 1.5 or more and less than 2), and organic substances such as acrylic resin, urethane resin, melamine resin, alkyd resin, and siloxane polymer. In particular, it is preferable to use a thermosetting resin made of a mixture of a melamine resin, an alkyd resin, and an organic silane condensate as the organic substance. The refractive index adjusting layer can be formed using the above materials by a coating method such as a gravure coating method or a bar coating method, a vacuum deposition method, a sputtering method, an ion plating method, or the like.

  The thickness of the refractive index adjustment layer 4 is preferably 10 nm to 200 nm, more preferably 20 nm to 150 nm, and further preferably 20 nm to 130 nm. If the thickness of the refractive index adjusting layer is too small, it is difficult to form a continuous film. Moreover, when the thickness of a refractive index adjustment layer is too large, there exists a tendency for the transparency of a transparent conductive film to fall or for a crack to arise easily in a refractive index adjustment layer. Further, if the refractive index adjusting layer is formed with such a nano-order thickness, the surface of the refractive index adjusting layer on the side of the transparent conductive layer 3 has a raised shape on the surface of the cured resin layer 2 that is the underlying layer. Maintain almost. And since the protruding shape is maintained also on the surface of the transparent conductive layer 3, and the protruding part 32 is formed, it can be set as the transparent conductive film which has blocking resistance and slipperiness.

  The refractive index adjusting layer may have nanoparticles having an average particle diameter of 1 nm to 500 nm. The content of the nanoparticles in the refractive index adjusting layer is preferably 0.1% by weight to 90% by weight. As described above, the average particle diameter of the nanoparticles used in the refractive index adjusting layer is preferably in the range of 1 nm to 500 nm, and more preferably 5 nm to 300 nm. Further, the content of the nano fine particles in the refractive index adjusting layer is more preferably 10% by weight to 80% by weight, and further preferably 20% by weight to 70% by weight. By containing nanoparticles in the refractive index adjusting layer, the refractive index of the refractive index adjusting layer itself can be easily adjusted.

  Examples of the inorganic oxide forming the nano fine particles include fine particles such as silicon oxide (silica), hollow nano silica, titanium oxide, aluminum oxide, zinc oxide, tin oxide, and zirconium oxide. Among these, fine particles of silicon oxide (silica), titanium oxide, aluminum oxide, zinc oxide, tin oxide, and zirconium oxide are preferable. These may be used alone or in combination of two or more.

<Transparent conductive film roll>
The transparent conductive film 10 of this embodiment can be a transparent conductive film wound body in which a long sheet is wound in a roll shape. The roll of the long sheet of the transparent conductive film uses a roll-shaped roll of the long sheet as the transparent polymer substrate, and adds the above-mentioned cured resin layer, transparent conductive layer, refractive index adjustment layer, etc. Any of the typical layers may be formed by a roll-to-roll process. In forming such a wound body, a protective film (separator) having a weak adhesive layer may be bonded to the surface of the transparent conductive film and then wound into a roll shape. Since the transparent conductive film has improved slipperiness and blocking resistance, it can form a wound sheet of a long sheet of transparent conductive film without using a protective film. That is, by improving slipperiness and blocking resistance, the occurrence of scratches on the film surface at the time of handling is suppressed and the film is easy to wind, so even without attaching a protective film to the surface, It is easy to obtain a wound body obtained by winding a long sheet into a roll. Thus, since the transparent conductive film of this embodiment can form the wound body of a long sheet, without using a protective film, it is excellent in workability | operativity at the time of using for formation of a subsequent touch panel, etc. Further, by eliminating the need for a protective film as a process member, it can contribute to cost reduction and waste reduction.

<Touch panel>
The transparent conductive film 10 can be suitably applied to, for example, a capacitive touch panel or a resistive touch panel.

  In forming the touch panel, another substrate such as glass or a polymer film can be bonded to one or both main surfaces of the transparent conductive film via a transparent adhesive layer. For example, you may form the laminated body by which the transparent base | substrate was bonded together through the transparent adhesive layer on the surface by which the transparent conductive layer 3 of the transparent conductive film is not formed. The transparent substrate may be composed of a single substrate film or may be a laminate of two or more substrate films (for example, laminated via a transparent adhesive layer). A hard coat layer can also be provided on the outer surface of the transparent substrate to be bonded to the transparent conductive film.

  The pressure-sensitive adhesive layer used for bonding the transparent conductive film and the substrate can be used without particular limitation as long as it has transparency. Specifically, for example, acrylic polymers, silicone polymers, polyesters, polyurethanes, polyamides, polyvinyl ethers, vinyl acetate / vinyl chloride copolymers, modified polyolefins, epoxy systems, fluorine systems, natural rubbers, rubbers such as synthetic rubbers, etc. Those having the above polymer as a base polymer can be appropriately selected and used. In particular, an acrylic pressure-sensitive adhesive is preferably used from the viewpoint that it is excellent in optical transparency, exhibits adhesive properties such as appropriate wettability, cohesiveness and adhesiveness, and is excellent in weather resistance and heat resistance.

  When the transparent conductive film according to the present invention is used for forming a touch panel, the handling property at the time of forming the touch panel is excellent. Therefore, a touch panel excellent in transparency and visibility can be manufactured with high productivity.

<Display element>
The transparent conductive film of the present embodiment can be suitably used as, for example, antistatic or electromagnetic wave shielding for a transparent member of various display elements such as a liquid crystal display element and a solid-state imaging element, liquid crystal light control glass, and a transparent heater. Since the raised portion on the outermost surface of the transparent conductive film of the present embodiment has a specific relationship with the opening size of the black matrix included in these display elements, a higher-definition display element can be obtained. it can.

<Image display device>
The image display apparatus of this embodiment has an image display element and the touch panel described above. The image display element generally includes a color filter having a black matrix on the viewing side of the image display cell, and a polarizing plate on the opposite side to the viewing side. As the image display cell, a liquid crystal cell, an organic EL cell, or the like can be used. By combining the touch panel according to this embodiment and various display elements, glare is suppressed, and a higher-definition image display device (for example, a liquid crystal touch panel) can be manufactured.

[Other Embodiments]

  In the embodiment shown in FIG. 1, the transparent conductive layer 3 is provided only on one first main surface 1 a side of the transparent polymer substrate 1, but is not limited thereto, and the other second main surface 1 b. It may also be provided on the side. In this case, as shown in FIG. 1, when the cured resin layer 2b is formed as a base layer, it is provided on the second main surface 1b side due to the base flat portion and the base raised portion of the cured resin layer 2b. A flat portion and a raised portion are also formed on the surface of the transparent conductive layer formed.

  As a method for forming the base raised portion of the cured resin layer, an appropriate method can be adopted in addition to a method of imparting a raised shape by dispersing particles in the cured resin layer as shown in FIG. For example, there may be mentioned a method in which a cured resin layer is separately applied on the cured resin layer, and a base raised portion is provided on the surface of the cured resin layer by a transfer method using a mold or the like. In addition, as much as possible, the surface of the film used for forming the cured resin layer is previously roughened by an appropriate method such as sandblasting, embossing roll, chemical etching, etc., to give a raised shape to the film surface. The method of forming the surface of the member itself which forms a cured resin layer as a base protruding part by a method etc. is mention | raised. These base ridges may be formed as a layer in which two or more methods are combined to combine base ridges in different states. Among the methods for forming the cured resin layer, a method of providing a cured resin layer in which particles are dispersedly dispersed is preferable from the viewpoints of ease of imparting shape and suppressing increase in haze.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to a following example, unless the summary is exceeded. In the examples, unless otherwise indicated, “parts” means “parts by weight”.

[Example 1]
It contains a plurality of monodisperse particles (trade name “SSX105” manufactured by Sekisui Jushi Co., Ltd.) having a mode particle diameter of 3.0 μm and a binder resin (trade name “Unidic ELS-888” manufactured by DIC Corporation), and the solvent is ethyl acetate. Next, the thickness after drying the coating composition using a gravure coater on one side of a long substrate having a thickness of 100 μm (trade name “ZEONOR” manufactured by Nippon Zeon Co., Ltd.) The coating was dried by heating at 80 ° C. for 1 minute. Then, the cured resin layer was formed by irradiating the ultraviolet-ray of the integrated light quantity 250mJ / cm < ² > with a high pressure mercury lamp. About the addition part of particle | grains, 0.07 part was added with respect to 100 parts of resin. In addition, the thickness of the base flat part of the cured resin layer is obtained from an average value of thicknesses measured at five points equally spaced in the film width direction using a spectrophotometer (trade name “MCPD2000” manufactured by Otsuka Electronics Co., Ltd.). Asked.

Next, on the surface of the cured resin layer, a refractive index adjusting agent (manufactured by JSR, trade name “OPSTAR KZ6661” was applied using a gravure coater, and the coating film was dried by heating at 60 ° C. for 1 minute. Then, the refractive index adjustment layer with a thickness of 100 nm and a refractive index of 1.65 was formed by irradiating an ultraviolet ray with an integrated light quantity of 250 mJ / cm ² with a high-pressure mercury lamp to form a refractive index adjustment layer having a refractive index of 1.65. And a long base material having a refractive index adjusting layer is put into a take-up type sputtering apparatus, and an indium tin oxide layer having a thickness of 27 nm (argon gas: 98% and argon gas) is formed on the surface of the refractive index adjusting layer as a transparent conductor layer. In an atmosphere of 0.4 Pa composed of 2% oxygen, sputtering using a sintered body composed of 97% by weight of indium oxide-3% by weight of tin oxide) and a copper layer having a thickness of 200 nm are sequentially stacked. At this time, the refractive index adjusting layer, the transparent conductive layer, and the metal layer were laminated along the base flat portion and the base raised portion of the cured resin layer, thereby producing a transparent conductive film.

[Example 2]
Except that monodisperse particles (manufactured by Nippon Shokubai Co., Ltd., trade name “Seahoster KE-P250”) having a mode particle diameter of 2.5 μm were used as particles, and the number of parts added to 100 parts of resin was 0.4 parts. A transparent conductive film was prepared in the same manner as in 1.

[Example 3]
Example 1 except that monodisperse particles (manufactured by Soken Co., Ltd., trade name “MX-180TA”) having a mode particle diameter of 1.8 μm were used as the particles, and the number of added parts relative to 100 parts of resin was 0.2 parts. Similarly, a transparent conductive film was produced.

[Example 4]
A transparent conductive film was produced in the same manner as in Example 3 except that a cured resin layer was formed on both sides of the long base material.

[Example 5]
The same as Example 1 except that monodispersed particles (trade name “XX134AA”, manufactured by Sekisui Jushi Co., Ltd.) having a mode particle diameter of 2.0 μm were used as the particles, and the number of added parts relative to 100 parts of resin was 0.2 parts. A transparent conductive film was prepared.

[Example 6]
Example 1 except that monodisperse particles (manufactured by Nippon Shokubai Co., Ltd., trade name “Seahoster KE-P150”) having a mode particle diameter of 1.5 μm are used as particles, and the number of added parts is 0.4 parts with respect to 100 parts of resin. A transparent conductive film was prepared in the same manner as in 1.

[Example 7]
Example 1 except that monodisperse particles having a mode particle diameter of 1.3 μm (trade name “SX-130H”, manufactured by Soken Co., Ltd.) were used as the particles, and the number of parts added to 100 parts of resin was 0.4 parts. Similarly, a transparent conductive film was produced.

[Example 8]
Using monodisperse particles (manufactured by Sekisui Resin Co., Ltd., trade name “XX121AA”) having a mode particle diameter of 3.5 μm as particles, the number of parts added per 100 parts of resin is 0.1 part, and the thickness of the cured resin layer after curing A transparent conductive film was produced in the same manner as in Example 1 except that the thickness was set to 2.0 μm.

[Comparative Example 1]
Transparent as in Example 1, except that monodisperse particles (manufactured by Sekisui Jushi Co., Ltd., trade name “XX83AA”) having a mode particle diameter of 5 μm were used as the particles, and the number of added parts relative to 100 parts of the resin was 0.1 parts. A conductive film was prepared.

[Evaluation]
The following evaluation was performed about each transparent conductive film obtained by the Example and the comparative example.

(Glare determination)
The produced transparent conductive film was cut into a 5 cm square and used as an evaluation sample. Separately, commercially available liquid crystal display devices each including a black matrix in which a rectangular opening (the shape shown in FIG. 2) having a minimum distance between two non-adjacent sides having the values shown in Table 1 are prepared. Placed on a flat table. Next, the evaluation sample was placed on the display surface of the display device with the evaluation surface (transparent conductive layer side) facing upward. Thereafter, a green background was displayed on the display surface of the display device, and the presence or absence of glare was evaluated by visual judgment from directly above the evaluation sample. The case where there was no glare was evaluated as “◯”, and the case where it was present was evaluated as “×”. The results are shown in Table 1.

(Minimum distance between two non-adjacent sides of the black matrix opening)
The minimum value of the distance between two non-adjacent sides of the opening of the black matrix of the liquid crystal display device in the glare determination (that is, the length of the short side of the opening shown in FIG. 2) is measured with a shape measuring laser microscope (Co., Ltd.). Measurement was carried out by Keyence Corporation, trade name “VK-8500”, magnification: 10 times. The results are shown in Table 1.

(Measurement of the maximum diameter of the cross-sectional shape of the ridge)
The surface shape of the transparent conductive layer side, which is the outermost surface layer of the evaluation sample prepared by the above-described glare determination, is measured with a non-contact type three-dimensional surface roughness meter (trade name “WYKO NT3300” manufactured by Veeco) with a field of view of 92 μm × 121 μm. The measurement was performed at a magnification of 50 times in the range. The raised portion in the obtained surface shape data was cut into a circle at a plane located at a height of 10 nm from the flat portion, and the maximum diameter of the cross-sectional shape obtained at that time was measured. In addition, it measured about both surfaces (the transparent conductive layer surface and the cured resin layer surface) with respect to the evaluation sample which concerns on Example 4. FIG. The results are shown in Table 1.

(Haze)
The haze of the produced transparent conductive film was measured using a haze meter (model number “HM-150” manufactured by Murakami Color Research Laboratory Co., Ltd.) in accordance with the haze (turbidity) of JIS K7136 (2000). The results are shown in Table 1.

(Blocking resistance)
About the produced transparent conductive film, a film having a smooth surface (trade name “ZEONOR film ZF-16” manufactured by Nippon Zeon Co., Ltd.) is pressure-bonded to the surface of the transparent conductive layer with finger pressure. Was visually confirmed according to the following criteria (number of specimens N = 10). The results are shown in Table 1.
<Evaluation criteria>
○: No sticking occurs.
Δ: Sticking once, but the film leaves when time passes.
X: The stuck film does not return to its original state.

  In the transparent conductive films obtained in the examples, the blocking resistance was good and the glare was suppressed even when combined with a high-definition liquid crystal display element exceeding 150 ppi. Moreover, the haze was 3 or less in all samples, and the transparency was excellent. On the other hand, in the transparent conductive film obtained in the comparative example, although the blocking resistance and haze were good results, glare occurred in combination with the high-definition liquid crystal display element, and it corresponds to the high-definition display element. The result is that you can not.

  As described above, in the transparent conductive films of Examples 1 and 2, glare is suppressed even in a high-definition liquid crystal display element exceeding 150 ppi. In the transparent conductive films of Examples 3 to 7, up to 324 ppi. It was also found that it can be applied to high-definition liquid crystal display elements. Accordingly, it can be seen that the smaller the maximum diameter near the bottom of the raised portion in the outermost surface layer corresponding to the miniaturization of the opening of the black matrix, the higher the resolution of the display element can be handled.

DESCRIPTION OF SYMBOLS 1 Transparent polymer base material 1a 1st main surface of a transparent polymer base material 1b 1st main surface of a transparent polymer base material 2a, 2b Cured resin layer 3 Transparent conductive layer 4 Refractive index adjustment layer 5 Particle 10 Transparent conductive film 11 Black matrix 21 Base flat portion 22 Base raised portion 31 Flat portion 32 Raised portion C ₁ , C ₂ Cross-sectional shape of raised portion d ₁ , d ₂ Cross-sectional maximum diameter L ₁ , L ₂ , L ₃ Not adjacent to opening Minimum value of distance between two sides O ₁ , O ₂ , O ₃ openings P A plane parallel to the flat part

Claims (11)

A transparent conductive film for a display element having a black matrix having a polygonal opening and having a definition of 150 ppi or more,
A transparent polymer substrate;
A transparent conductive layer provided on the first main surface side of the transparent polymer substrate;
A cured resin layer provided between the transparent polymer substrate and the transparent conductive layer and on at least one of the second principal surface opposite to the first principal surface of the transparent polymer substrate;
The outermost surface layer on which the cured resin layer is formed has a flat portion and a raised portion on the surface,
The height of the raised portion is larger than 10 nm from the flat portion,
The maximum diameter of the cross-sectional shape formed by intersecting the raised portion at a position parallel to the flat portion at a distance of 10 nm from the flat portion is based on the minimum value of the distance between two non-adjacent sides of the opening of the black matrix. A small transparent conductive film. The cured resin layer has a base flat portion and a base raised portion on the surface,
The transparent conductive film according to claim 1, wherein the flat portion of the outermost surface layer is caused by the base flat portion, and the raised portion is caused by the base raised portion. The cured resin layer includes particles,
The transparent conductive film according to claim 2, wherein the base raised portion is formed due to the particles.   The thickness of the base flat part of the said cured resin layer is a transparent conductive film of Claim 3 smaller than the mode particle diameter of the said particle | grain. The cured resin layer is provided between the transparent polymer substrate and the transparent conductive layer,
The transparent conductive film according to any one of claims 1 to 4, further comprising a refractive index adjusting layer between the cured resin layer and the transparent conductive layer.   Haze is 5% or less, The transparent conductive film of any one of Claims 1-5.   The transparent conductive film of any one of Claims 1-6 further equipped with the transparent conductive layer provided in the 2nd main surface side on the opposite side to the 1st main surface side of the said transparent polymer base material.   The transparent conductive film winding body by which the elongate sheet | seat of the transparent conductive film of any one of Claims 1-7 was wound by roll shape.   A touch panel provided with the transparent conductive film of any one of Claims 1-7.   A display element having a resolution of 150 ppi or more, comprising the transparent conductive film according to claim 1.   An image display device in which a display element having a definition of 150 ppi or more and the touch panel according to claim 9 are stacked.

Images